Self-assembled highly crystalline TiO

2
mesostructures for
sunlight-driven, pH-responsive photodegradation of dyes
Xinyi Zhang
a,b,
*, Jianfeng Yao
c
, Dan Li
c
, Xiaodong Chen
c
, Huanting Wang
c
,
Leslie. Y. Yeo
d
, James. R. Friend
b,d,
*
a
School of Chemistry, Monash University, Clayton, VIC 3800, Australia
b
Melbourne Centre for Nanofabrication, Clayton, VIC 3800, Australia
c
Department of Chemical Engineering, Monash University, Clayton, VIC 3800, Australia
d
Micro/Nanophysics Research Laboratory, RMIT University, Melbourne, VIC 3000, Australia
A R T I C L E I N F O
Article history:
Received 16 July 2013
Received in revised form 26 December 2013
Accepted 31 March 2014
Available online 04 April 2014
Keywords:
A. Semiconductor
A. Oxide
C. Transmission electron microscopy (TEM)
D. Crystal structure
D. Catalytic properties
A B S T R A C T
The development of new strategies and photocatalytic materials for practical environmental solutions
remains a great challenge, particularly due to the large energy demands associated with various
remediation processes. In this paper, we report the fabrication of self-assembled ordered mesoporous
TiO
2
with highly crystalline anatase structures as well as high surface area, and characterize their
photocatalytic performance on the degradation of three typical dyes, including anionic methyl orange,
cationic methylene blue, and neutral rhodamine B driven merely by sunlight. The results show that the
dye photodegradation strongly depends on the charging state of both mesoporous TiO
2
surface and dyes,
which can be adjusted by the pH value of the solutions. Such charge-dependent photocatalytic
functionality of mesoporous TiO
2
can thus be exploited for highly efcient and selective dye
photodegradation.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Dyes are common across many industriesincluding printing,
textile, pulp and paper, and leather processingto color products
to suit customer desires, generating substantial amounts of dye
wastewater that is harmful to the environment, hazardous to
human health, and difcult to degrade by natural means. Their use
remains problematic, an anachronism remaining among the many
chemicals produced and used via sustainable processes developed
in recent years. Numerous treatment technologies have been
developed to treat dye wastewater, from physico-chemical to
biological processes [16]. Among these, the solar energy-driven
photodegradation of dyes in aqueous solutions has gained
considerable attention due to practical and fundamental benets
alike in recognition of the impact dye-laden waste has on the
environment [710]. Semiconductor-based photocatalysis has
attracted particular attention as a suitable green technology
for this purpose because of its chemical stability and favorable
energy band structure. TiO
2
is considered to be one of the best
material candidates for photovoltaic and photocatalytic devices in
this application; its nanoparticles possess superior photocatalytic
efciency over the bulk phase and the photocatalytic activity of
such nanoparticles have been extensively investigated [1113].
However, intrinsic limitations prevent further improvement in the
photocatalytic process in TiO
2
nanoparticles. Illuminated TiO
2
nanoparticles behave as short-circuited electrodes: the interfacial
charge transfer competing with the charge recombination
between the charge carriers is a major problem in photocatalysis
and is a limiting factor in improving the photocatalytic efciency
[14]. There are further drawbacks: nanoparticles tend to aggregate,
are difcult to separate and recover from solution, and the
environmental impact of such nanoparticles remains an open
question, greatly limiting their practical use in many commercial
applications. The signicant need remains, therefore, for another
approach and alternative materials to solve these challenging
problems inherent in TiO
2
and in using them in a nanoparticle
morphology.
So far, little information is available on the reaction mecha-
nisms involved in the photocatalytic degradation of dyes and on
the identication of major transient intermediates which have
been more recently recognized as very important aspects of these
processes, especially from the viewpoint of practical application
[1517]. As the charging states of both dye and photocatalyst play
* Corresponding author. Tel.: +61 3 9902 4619; fax: +61 3 9905 4597.
E-mail addresses: xinyi.zhang@monash.edu (X. Zhang),
james.friend@rmit.edu.au (J.R. Friend).
http://dx.doi.org/10.1016/j.materresbull.2014.03.036
0025-5408/ 2014 Elsevier Ltd. All rights reserved.
Materials Research Bulletin 55 (2014) 1318
Contents lists available at ScienceDirect
Materials Research Bulletin
j our nal homepage: www. el se vi e r . com/ l ocat e/ mat r esbu
crucial roles in the photodegradation process, investigating the
prior adsorption of dyes in addition to the interactions between the
dyes and the catalyst surface is crucially important to develop
superior photocatalysts for efcient dye degradation. In compari-
son with TiO
2
nanoparticles, highly structured mesoporous TiO
2
formed using evaporation-induced self-assembly is of consider-
able interest [1820]. The advantage of this technique lies in the
possibility of tuning the symmetry of the mesostructure by
adjusting the composition of the initial solution and the
preparation condition [2123]. Further, the mesoporous morphol-
ogy avoids the myriad practical drawbacks of nanoparticles. To the
best of our knowledge, there is no study to date on the pH-
responsively selective photocatalytic activity of ordered meso-
porous TiO
2
. Here, we report the fabrication of self-assembled
highly crystalline ordered mesoporous TiO
2
and investigate the
sunlight-driven photocatalytic activity of the mesoporous TiO
2
.
The results show that the adsorption of dyes on the mesoporous
TiO
2
surface strongly depends on the pH value of the dye solution
in addition to the charging state of the dyes, and that these factors
in turn have a crucial effect on the photocatalytic performance of
the mesoporous TiO
2
.
2. Experimental
Mesoporous TiO
2
was synthesized by using a mixture of poly
(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)
copolymer (P123), ethanol, concentrated HCl, and tetrabutyl
titanate (TBT) [24]. The mass ratio of P123/TBT/EtOH/HCl was
1:2.8:30:2. For a typical synthesis, 1.0 g of P123 was dissolved in
30 g of ethanol, and then 2 g of concentrated HCl was slowly added
with stirring. Then 2.8 g of TBT was added, and the solution was
stirred for 4 h. The resulting solutions were transferred into Petri
dishes and subsequently sealed and aged at room temperature for
1 week. Then the samples were calcined at 400

C in air for 2 h with

a 1

C min
1
temperature ramp to obtain the mesoporous TiO
2
thin
lms with thickness of about 2 mm. All chemical reagents used in
this study were of analytical grade and were supplied by Sigma
Aldrich (Australia). Nitrogen adsorptiondesorption experiments
were performed at 77 K with a Micromeritics ASAP 2020MC. The
samples were degassed at 300

C for 5 h prior to measurement.

The pore volume was estimated from the desorption branch of the
isotherm at P/P
o
= 0.98 assuming complete pore saturation. The
morphology and microstructure of the mesoporous TiO
2
were
investigated using an X-ray diffractometer (XRD, PW1140/90) with
CuKa radiation (25 mA and 40 kV), and a transmission electron
microscope (TEM, JEOL-2011).
Three typical dyes including rhodamine B (RB), methyl orange
(MO), and methylene blue (MB) were studied for photodegrada-
tion. The molecule structures of the dyes are shown in Fig. 1. The
concentrations of the dye solutions were 50 mg/L. 10 mg of the
mesoporous TiO
2
samples were added into 20 mL dye solution and
the muddy solution was dispersed with an ultrasonic instrument
for 30 min, and then irradiated by sunlight. The temperature was in
the range of 2226

C and the average sunlight intensity was about

6.5 kW h m
2
. The pH of the samples was adjusted by using
0.1 mol/L HCl or 0.1 mol/L NaOH. After the photocatalytic experi-
ment, the remaining dye solutions were collected and analyzed. A
UV-240 UVvis spectrometer was used to record the change of the
absorbance of the dye solution.
3. Results and discussion
The TiO
2
mesostructures were formed using the evaporation
induced self-assembly (EISA) approach, which has been estab-
lished as an efcient process for the preparation of mesostructured
oxide with controlled morphologies [24]. The wide-angle X-ray
diffraction pattern of the sample is shown in Fig. 2a. The main
diffraction peaks correspond to the tetragonal structure of anatase
TiO
2
. Fig. 2b exhibits the small angle X-ray diffraction spectrum,
clearly showing the principle diffractional peak (10 0) and
suggesting a well-dened hexagonal mesostructure. The N
2
sorption isotherms of mesoporous TiO
2
show type-IV curves with
clear condensation steps, indicating uniform mesopores (Fig. 2c).
The Langmuir surface area which is calculated from nitrogen
sorption results to be 172.2 m
2
/g. Fig. 2d shows the derived pore
size distributions. The pore size distributions of the samples are
observed to be narrow and the corresponding peak is located at
about 4.8 nm, conrming the formation of the mesostructure [25].
The mesostructure of the TiO
2
was further investigated by
transmission electron microscopy (TEM). The TEM images of the
ordered mesoporous structure of the TiO
2
are displayed in Fig. 3. As
shown in Fig. 3a, the cross-sectional view of the mesoporous TiO
2
Fig. 1. The molecule structures of dyes.
14 X. Zhang et al. / Materials Research Bulletin 55 (2014) 1318
exhibits parallel cylindrical channels. Fig. 3b shows the plain view
of the mesoporous TiO
2
, where ordered hexagonally-organized
mesopores with pore sizes of 35 nm can be clearly observed. The
inset in Fig. 3b shows the corresponding electron diffraction (ED)
pattern and the strong and continuous rings can be indexed as the
anatase TiO
2
structure, which is in accordance with the X-ray
diffraction (XRD) analysis. The high-resolution TEM (HRTEM)
images of the mesopore wall in the mesoporous TiO
2
are displayed
in Fig. 3c and d wherein the well-recognized lattice spacings of
0.35 and 0.19nm correspond to the anatase (10 1) and (2 0 0)
20 30 40 50 60
2
0
4
2
1
3
2
1
1
1
0
5
2
0
0
1
0
3
,

0
0
4
2 theta (degree)
1
0
1
1 2 3 4 5
2theta (degree)
100
0.0 0.2 0.4 0.6 0.8 1.0
0
20
40
60
80
100
120
140
160
180
200
220
A
d
s
o
r
p
t
i
o
n

V
o
l
u
m
e

(
c
m
3
g
-
1
)
Relative Presure (P/P
o
)
0 20 40 60 80 100 120 140 160
0.00
0.01
0.02
0.03
0.04
0.05
0.06
d
V
/
d
D
(
c
m
3
g
-
1
n
m
-
1
Pore size (nm)
(a) (b)
(c) (d)
Fig. 2. (a) Wide-angle and (b) small-angle XRD spectrum. (c) The N
2
sorption isotherm and (d) pore size distribution of mesoporous TiO
2
.
Fig. 3. TEM images show (a) the cross section, and, (b) plane view and HRTEM images show (c) the cross sectional view, and, (d) the plane view of the mesoporous TiO
2
.
X. Zhang et al. / Materials Research Bulletin 55 (2014) 1318 15
atomic planes, respectively. The interpore distance is about 6 nm,
which is consistent with the lattice parameter (6 nm) of the
hexagonal mesophase of the P123 liquid crystal.
Fig. 4 shows the sunlight-driven photocatalytic degradation of
dyes on mesoporous TiO
2
in neutral solutions (pH 6.5). The
adsorption spectra of RB, MB, and MO dyes at various irradiation
times on mesoporous TiO
2
are shown in Fig. 4a, b, and c,
respectively. As illustrated in Fig. 4d, the photocatalytic degrada-
tion of different dyes on mesoporous TiO
2
is quite different
(Fig. 4d). The degradation rates of dyes are in the order of
MO < MB < RB. Among them, the highest activity with a degrada-
tion rate of around 51% was obtained for RB after 1 h of sunlight
irradiation. The degradation mechanism of dyes under sunlight
irradiation is clearly different from that under UV irradiation.
During UV irradiation, electron (e

)hole (h
+
) pairs are generated
and are capable of initiating oxidation and reduction reactions on
the surface of TiO
2
[26,27]. The dyes are aromatic compounds
containing aryl rings which have delocalized electron systems.
These are responsible for the absorption of electromagnetic
radiation of varying wavelengths; the cleavage of conjugated
chromophore structures occuring during the photodegradation
process. Under sunlight irradiation, electron transfer to the TiO
2
surface is achieved mainly through the extraction of electrons from
excited dyes to the conduction band of TiO
2
directly or photo-
generated holes from the dyes to the valence band of TiO
2
,
respectively. The dyes with labile organic functional groups are
more easily to be excited and converted to the dye radicals that
subsequently undergo degradation. The dye radicals readily react
with hydroxyl ions undergoing oxidation or interacts effectively
with O
2
.
, HO
2
.
or HO
.
species to yield intermediates that
ultimately lead to CO
2
. The mechanism of solar light-induced
photocatalytic degradation of dyes is schematically presented in
Fig. 5. In neutral solutions, the differences in the ease of formation
of the dye radical and the stability of the aryl rings should be
300 350 400 450 500 550 600
0.0
0.5
1.0
1.5
2.0
2.5
3.0
A
b
s
o
r
b
a
n
c
e
Wavelength (nm)
0 h
1 h
2 h
4 h
6 h
a
400 500 600 700 800
0.0
0.5
1.0
1.5
2.0
2.5
3.0
c
A
b
s
o
r
b
a
n
c
e

Wavelength (nm)
0 h
1 h
2 h
4 h
6 h
300 400 500 600 700 800
0
1
2
b
A
b
s
o
r
b
a
n
c
e
Wavelength (nm)
0 h
1 h
2 h
4 h
6 h
0 1 2 3 4 5 6
0
20
40
60
80
100
d
D
e
g
r
a
d
a
t
i
o
n

r
a
t
e

(
%
)
Time (h)
Rb
MB
MO
Fig. 4. The adsorption spectra of (a) RB, (b) MB, and (c) MO dyes at various irradiation times on mesoporous TiO
2
, and (d) the photocatalytic degradation rate of the dyes on
mesoporous TiO
2
as a function of irradiation time in neutral solutions.
Fig. 5. Schematic illustration of sunlight-driven photocatalytic mechanism of dye
degradation on mesoporous TiO
2
.
16 X. Zhang et al. / Materials Research Bulletin 55 (2014) 1318
mainly responsible for the difference in the degradation rates
among the dyes [28,29]. As shown in Fig. 6, the photocatalytic
performance of mesoporous TiO
2
is strongly dependent on the pH
of the dye solutions. The photodegradation rate of MO is observed
to decrease with increasing pH, whereas the photodegradation
rate of MB is seen to increase with increasing pH. In contrast, the
photodegradation rate of RB also increases with increasing pH
though its degradation rate nevertheless drops signicantly in
strong alkaline solution. The adsorption of dyes on the surface of
catalysts is indispensable for photocatalytic degradation. There-
fore, the charging state of the dyes and catalyst surface should be
taken into consideration. Fig. 7 shows the z-potential of
mesoporous TiO
2
surface in aqueous solution with different pH
values. The TiO
2
surface is positively charged at pH 8 or below and
becomes negatively charged upon increasing the pH. Since MO is
an anionic dye containing sulphonate group whereas MB is a
cationic dye containing amino groups, it can then be inferred that
the cationic dye MB prefers to adsorb on the catalyst surface at pH
above 8, while the anionic dye MO prefers to adsorb on the catalyst
surface at pH lower than 8. The charging states of both the TiO
2
and dyes change when the pH of the solution changes. The
increase of pH decreases the positive charging of the TiO
2
surface.
For the anionic MO dye, the increase of pH then decreases the
attraction between anionic MO molecules and the TiO
2
surface,
especially on negatively charged TiO
2
surfaces at high pH. Besides,
the increase in pH also leads to an increase in the competition
between OH

and MO during their adsorption onto the catalyst

surface. These factors then lead to the decrease of degradation
rates of MO with increasing pH. For MB, on the other hand, the
increase in pH decreases the repulsion between the cationic MB
molecules and the TiO
2
surface whilst also enhancing the base-
catalyzed demethylation of MB [30]. Therefore, the degradation
rate of MB is seen to increase with increasing pH. RB, in contrast, is
positively charged, neutral, and negatively charged in the pH range
below 6.0, 6.0 to 10.8, and above 10.8, respectively [31]. At low pH,
the situation for RB is similar to that for MB, and hence the
degradation rate of RB is very low because of the difculty of the
adsorption. An increase in pH, however, decreases the positive
charging of both the TiO
2
surface and RB. The degradation of
neutral RB molecules then suggests that the adsorption of RB can
be achieved via hydrogen bonding or van der Waals forces in
neutral solution. Conversely, both TiO
2
surface and RB molecules
are negatively charged at strong alkaline solution (pH > 10.8)
and therefore the repulsion between the TiO
2
surface and anionic
RB molecules suppresses the adsorption and hence the degrada-
tion of RB.
4. Conclusions
In conclusion, ordered mesoporous TiO
2
with highly crystalline
walls and large surface area has been prepared and characterized.
The sunlight-driven photocatalytic degradation of various dyes on
mesoporous TiO
2
and the role of pH in the photocatalytic
degradation process was then systematically investigated. We
demonstrate that the photocatalytic activity of mesoporous TiO
2
is
strongly pH-responsive, and can therefore be controlled by
adjusting the pH of the aqueous solutions. All of the dyes were
shown to be effectively photocatalytic degraded on mesoporous
TiO
2
by selecting a suitable pH range. This work therefore shows
the potential of heterogeneous photocatalysis to decontaminate
dye wastewater and opens up a new way for designing sunlight-
driven photocatalysts for environmental remediation.
Acknowledgements
This work was supported by the Australian Research Council
(ARC) (Grant No.: DP120104334) and Monash University. This work
was performed in part at the Melbourne Centre for Nano-
fabrication (MCN) in the Victorian Node of the Australian National
Fabrication Facility (ANFF).
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